On-line monitoring of chemical reactions by using bench-top nuclear magnetic resonance spectroscopy.

Real-time nuclear magnetic resonance (NMR) spectroscopy measurements carried out with a bench-top system installed next to the reactor inside the fume hood of the chemistry laboratory are presented. To test the system for on-line monitoring, a transfer hydrogenation reaction was studied by continuously pumping the reaction mixture from the reactor to the magnet and back in a closed loop. In addition to improving the time resolution provided by standard sampling methods, the use of such a flow setup eliminates the need for sample preparation. Owing to the progress in terms of field homogeneity and sensitivity now available with compact NMR spectrometers, small molecules dissolved at concentrations on the order of 1 mmol L(-1) can be characterized in single-scan measurements with 1 Hz resolution. Owing to the reduced field strength of compact low-field systems compared to that of conventional high-field magnets, the overlap in the spectrum of different NMR signals is a typical situation. The data processing required to obtain concentrations in the presence of signal overlap are discussed in detail, methods such as plain integration and line-fitting approaches are compared, and the accuracy of each method is determined. The kinetic rates measured for different catalytic concentrations show good agreement with those obtained with gas chromatography as a reference analytical method. Finally, as the measurements are performed under continuous flow conditions, the experimental setup and the flow parameters are optimized to maximize time resolution and signal-to-noise ratio.

Highly stable and finely tuned magnetic fields generated by permanent magnet assemblies.

Permanent magnetic materials are the only magnetic source that can be used to generate magnetic fields without power consumption or maintenance. Such stand-alone magnets are very attractive for many scientific and engineering areas, but they suffer from poor temporal field stability, which arises from the strong sensitivity of the magnetic materials and mechanical support to temperature variation. In this work, we describe a highly efficient method useful to cancel the temperature coefficient of permanent magnet assemblies in a passive and accurate way. It is based on the combination of at least two units made of magnetic materials with different temperature coefficients arranged in such a way that the ratio of the fields generated by each unit matches the ratio of their effective temperature coefficients defined by both the magnetic and mechanical contributions. Although typically available magnetic materials have negative temperature coefficients, the cancellation is achieved by aligning the fields generated by each unit in the opposite direction. We demonstrate the performance of this approach by stabilizing the field generated by a dipolar Halbach magnet, recently proposed to achieve high field homogeneity. Both the field drift and the homogeneity are monitored via nuclear magnetic resonance spectroscopy experiments. The results demonstrate the compatibility of the thermal compensation approach with existing strategies useful to fine-tune the spatial dependence of the field generated by permanent magnet arrays.

Multiecho sequence for velocity imaging in inhomogeneous rf fields.

The unambiguous determination of velocities with spatial resolution in a multiecho PFG NMR sequence strongly depends on the homogeneity of the B1 field. This affects, in particular, the use of surface coils that bear considerable potential for on-line flow monitoring where a fast-imaging sequence can become vital. However, even with most rf coils dedicated for imaging applications, B1 inhomogeneities are sufficiently large to generate severe problems in performing velocity-imaging experiments. In this paper, the use of a combination of different phase cycles in Carr-Purcell sequences is discussed. The suggested phase cycling scheme tolerates large flip angle imperfections arising in inhomogeneous B1 fields, and thus allows acquisition of a maximum number of echoes within a pulse train. The performance of the velocity-imaging sequence is proven by using phantom samples developing known laminar flow patterns.

Single-sided sensor for high-resolution NMR spectroscopy.

The unavoidable spatial inhomogeneity of the static magnetic field generated by open sensors has precluded their use for high-resolution NMR spectroscopy. In fact, this application was deemed impossible because these field variations are usually orders of magnitude larger than those created by the microscopic structure of the molecules to be detected. Recently, chemical shift resolved NMR spectra were observed for the first time outside a portable single-sided magnet by implementing a method that exploits inhomogeneities in the rf field designed to reproduce variations of the static magnetic field. In this communication, we describe in detail the magnet system built from permanent magnets as well as the rf coil geometry used to compensate the static field variations.

Self-diffusion measurements by a mobile single-sided NMR sensor with improved magnetic field gradient.

A simple and fast method of measuring self-diffusion coefficients of protonated systems with a mobile single-sided NMR sensor is discussed. The NMR sensor uses a magnet geometry that generates a highly flat sensitive volume where a strong and highly uniform static magnetic field gradient is defined. Self-diffusion coefficients were measured by Hahn- and stimulated echoes detected in the presence of the uniform magnetic field gradient of the static field. To improve the sensitivity of these experiments, a Carr-Purcell-Meiboom-Gill pulse sequence was applied after the main diffusion-encoding period. By adding the echo train the experimental time was strongly shortened, allowing the measurement of complete diffusion curves in less than 1min. This method has been tested by measuring the self-diffusion coefficients D of various organic solvents and poly(dimethylsiloxane) samples with different molar masses. Diffusion coefficients were also measured for n-hexane absorbed at saturation in natural rubber with different cross-link densities. The results show a dependence on the concentration that is in good agreement with the theoretical prediction. Moreover, the stimulated-echo sequence was successfully used to measure the diffusion coefficient as a function of the evolution time in systems with restricted diffusion. This type of experiment proves the pore geometry and gives access to the surface-to-volume ratio. It was applied to measure the diffusion of water in sandstones and sheep Achilles tendon. Thanks to the strong static gradient G(0), all diffusion coefficients could be measured without having to account for relaxation during the pulse sequence.

Profiles with microscopic resolution by single-sided NMR.

A single-sided NMR sensor to produce depth profiles with microscopic spatial resolution is presented. It uses a novel permanent magnet geometry that generates a highly flat sensitive volume parallel to the scanner surface. By repositioning the sensitive slice across the object one-dimensional profiles of the sample structure can be produced with a space resolution better than 5 microm. The open geometry of the sensor results in a powerful testing tool to characterize arbitrarily sized objects in a non-destructive way.

Velocity imaging by ex situ NMR.

A pulsed field gradient stimulated spin-echo NMR sequence is combined with imaging methods to spatially resolve velocity distributions and to measure 2D velocity maps ex situ. The implementation of these techniques in open sensors provides a powerful non-invasive tool to measure molecular displacement in a large number of applications inaccessible to conventional closed magnets. The method is implemented on an open tomograph that provides 3D spatial localization by combining slice selection in the presence of a uniform static magnetic field gradient along the depth direction with pulsed field gradients along the two lateral directions. Different pipe geometries are used to demonstrate that the sequence performs well even in the extremely inhomogeneous B0 and B1 fields of these sensors.

Multispin moments edited by multiple-quantum NMR: application to elastomers.

The spin system response to the five-pulse sequence used for measurements of double-quantum and triple-quantum buildup curves is evaluated in the initial excitation/reconversion regime. The multispin dipolar network that is present also in many soft solids like elastomers was considered. It is proved rigorously that the relevant quantity for analysis of double-quantum build-up curves in the initial regime is the second van Vleck moment. The higher-order moments edited by double-quantum as well as higher-order coherences in the multiple-quantum build-up experiments are different from van Vleck moments. These results can be applied to compare (1)H residual moments edited by double-quantum and triple-quantum experiments with those measured by other NMR methods. The sensitivity of multiple-quantum coherences to the changes in the values of residual dipolar couplings for cross-linked natural rubber under uniaxial elongation is also discussed. Under such conditions (1)H second van Vleck moments were measured for different elongation ratios of a cross-linked natural rubber. Moreover, (1)H triple-quantum edited moments were also measured for the same sample under uniaxial compression. The dependence of the second van Vleck moment and the time of the maximum of the double-quantum buildup curve on the cross-link density of natural rubber measured at low magnetic field was also investigated.

Velocity distributions remotely measured with a single-sided NMR sensor.

The pulsed field gradient nuclear magnetic resonance (PFG NMR) method has proved to be a powerful non-invasive technique to measure molecular displacement in various systems. It has been largely implemented with conventional NMR magnets where the volume for housing the flow setup is restricted. In this work we present the first approach to measure velocity distributions ex situ implementing a pulsed field gradient sequence on a single-sided NMR sensor. The open geometry of these sensors provides access to NMR measurements of a large number of applications previously excluded by the geometry of conventional closed magnets. Both, the distortions to the displacement encoding observed when implementing a PFG sequence in the presence of strongly inhomogeneous B0 and B1 fields, and the performance of the modifications proposed to eliminate these distortions are shown by means of numerical simulations. An alternating stimulated spin-echo PFG sequence implemented to remotely measure velocity distributions was combined with a multi-echo acquisition scheme to significantly increase the sensitivity of the method. The technique was implemented to measure the velocity propagator in a fluid undergoing laminar flow and good agreement with the theoretical result is observed.

3D imaging with a single-sided sensor: an open tomograph.

An open tomograph to image volume regions near the surface of large objects is described. The central achievement in getting such a tomograph to work is the design of a fast two-dimensional pure phase encoding imaging method to produce a cross-sectional image in the presence of highly inhomogeneous fields. The method takes advantage of the multi-echo acquisition in a Carr-Purcell-Meiboom-Gill (CPMG)-like sequence to significantly reduce the experimental time to obtain a 2D image or to spatially resolve relaxation times across the sensitive volume in a single imaging experiment. Depending on T(2) the imaging time can be reduced by a factor of up to two orders of magnitude compared to the one needed by the single-echo imaging technique. The complete echo train decay has been also used to produce T(2) contrast in the images and to spatially resolve the T(2) distribution of an inhomogeneous object, showing that variations of structural properties like the cross-link density of rubber samples can be distinguished by this method. The sequence has been implemented on a single-sided sensor equipped with an optimized magnet geometry and a suitable gradient coil system that provides two perpendicular pulsed gradient fields. The static magnetic field defines flat planes of constant frequency parallel to the surface of the scanner that can be selected by retuning the probe frequency to achieve slice selection into the object. Combining the slice selection obtained under the presence of the static gradient of the open magnet with the two perpendicular pulsed gradient fields, 3D spatial resolution is obtained.

Multi-echo imaging in highly inhomogeneous magnetic fields.

A new pulsed field gradient multi-echo imaging technique to encode position in the phase of every echo generated by a CPMG sequence in the presence of a strongly inhomogeneous static magnetic field is presented. It was applied to improve the sensitivity in an imaging experiment by adding the echo train acquired during the CPMG sequence and to spatially resolve relaxation times of inhomogeneous specimens using single-sided probes. The sequence was implemented in a new bar-magnet MOUSE equipped with a gradient coil system to apply a pulsed magnetic field with a constant gradient along one spatial coordinate. An important reduction by a factor larger than two orders of magnitude in the acquisition time was obtained compared to the previously published single-point imaging technique.

Echo-planar rotating-frame imaging.

A new rotating-frame imaging method that produces a complete cross section of an object in a single experiment is reported. The echo planar rotating frame imaging (EPROFI) technique uses two perpendicular RF gradients for two-dimensional spatial encoding and fully exploits the formation of rotary echoes for fast sampling of spatial frequencies. The acquisition scheme yields the Fourier transform of the spin distribution on Cartesian coordinates for straightforward image reconstruction. Implementation of the technique on a low-field portable NMR probe is described and results are presented for test objects with different geometries.

Solid state proton imaging detected by quadrupole resonance.

A double resonance method for imaging of solid materials containing quadrupole nuclei via the coupled protons is reported. The technique uses a static field gradient to encode the position on the protons and the method of double resonance spin-echo to detect the occurrence of proton resonances by affecting the zero-field echo signal from the quadrupole system. The double resonance imaging method offers the advantages of higher spatial resolution and straightforward image reconstruction for powder samples compared with rotating-frame and Zeeman-perturbated nuclear quadrupole resonance encoding techniques.